CN109705466A - The excellent glass fiber reinforced polypropylene composite material and preparation method thereof of a kind of low haze, heat-proof aging - Google Patents
The excellent glass fiber reinforced polypropylene composite material and preparation method thereof of a kind of low haze, heat-proof aging Download PDFInfo
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- CN109705466A CN109705466A CN201811635152.3A CN201811635152A CN109705466A CN 109705466 A CN109705466 A CN 109705466A CN 201811635152 A CN201811635152 A CN 201811635152A CN 109705466 A CN109705466 A CN 109705466A
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- Prior art keywords
- glass fiber
- fiber reinforced
- heat
- low haze
- reinforced polypropylene
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 40
- -1 polypropylene Polymers 0.000 title claims abstract description 36
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 34
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 230000032683 aging Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 239000003463 adsorbent Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 9
- 150000003384 small molecules Chemical class 0.000 claims abstract description 8
- 150000002989 phenols Chemical class 0.000 claims abstract description 7
- 150000003568 thioethers Chemical class 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 229920005629 polypropylene homopolymer Polymers 0.000 claims abstract description 5
- 238000012360 testing method Methods 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 239000002156 adsorbate Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 17
- 239000003595 mist Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229920005633 polypropylene homopolymer resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses the excellent glass fiber reinforced polypropylene composite materials and preparation method thereof of a kind of low haze, heat-proof aging, its composition matches by weight percent are as follows: polypropylene 40%~85%, glass fibre 10~50%, compatilizer 2~10%, adsorbent 0.5-2%, antioxidant 0.2%~1%.Present invention has an advantage that passing through the low homopolypropylene for melting finger in selecting, the efficient low Hinered phenols distributed and thio ethers composite antioxidant, add natural aluminosilicate hydrochlorate adsorbent, the small-molecule substance effectively generated in absorption raw material process, reaches lamp body for the high request of material low haze；Simultaneously by selecting thermal stability more preferably compatilizer, in conjunction with efficient composite antioxidant, make sample obtained that there is superior ageing-resistant performance.
Description
Technical field
The present invention relates to a kind of PP composite material, the excellent glass of a kind of low haze, heat-proof aging is related in particular to
Glass fiber reinforced polypropylene composite material and preparation method.
Background technique
In recent years, with the requirement of automotive light weight technology, the dosage of plastics in the car increases year by year.Glass fiber reinforced polyester
Propylene (PP) material, since it is small with density, cost performance is high, heat resistance and resistant to chemical etching and stress crack resistant are excellent, easy
In the molding the features such as, and it is widely used in each position of automobile.But as consumer requires not vehicle product quality
Disconnected to improve, sporadic to the mist degree of automotive glass fiber reinforced polypropylene more stringent requirements are proposed.Glass fiber reinforced polyester
Being mainly derived from for propylene material volatile materials remaining in acrylic resin has lower-molecular substance, small molecule antioxidant, phase
Hold that agent, finishing agent for glass fibre, low molecule carbochain and aldoketones etc. produced by polymer degradation with aging are volatile in process
Property substance etc..The haze value of VW-50180 standard requirements automotive interior material is less than 200 μ g/g, most of glass fiber reinforced polyester
The material of propylene can be accomplished substantially.And lamp material has particular/special requirement, VW-50181 standard requirements car light for light transmittance
The haze value of case material is not able to satisfy this high request less than 50 μ g/g, conventional glass fiber reinforced polypropylene material, because
This develops low haze glass fiber reinforced polypropylene and is of great significance.
Glass fiber reinforced polypropylene material is commonly used in the structural member of stress, in the automobile long period service life time limit
Interior, glass fiber reinforced polypropylene material generates peroxide since certain chemical reactions can occur for damp and hot, oxygen influence, breaks
Free radical is formed after splitting, and further causes macromolecular chain cracking, branching, crosslinking, MODIFIED PP is made to lose the feature of high molecular material,
Therefore a certain number of antioxidant can be added in the production process of glass fiber reinforced polypropylene.However, this micromolecular antioxygen
Agent can slowly migrate out in the use process of part causes piece surface precipitation to whiten, and then influences beauty, therefore improve
Small molecule antioxidant formula system, slows down or eliminates the migration of antioxidant, and the good ageing-resistant performance of material is maintained to have
Significance.
Summary of the invention
The purpose of the present invention is to provide the excellent glass fiber reinforced polypropylene composite woods of a kind of low haze, heat-proof aging
Material and preparation method thereof.
The technical solution adopted by the present invention to solve the technical problems is: the excellent glass of a kind of low haze, heat-proof aging
Fiber reinforced polypropylene composite material, composition match by weight percent are as follows:
The acrylic resin be in the low homopolypropylene for melting finger, melt index under 230 DEG C/2.16KG test condition
MFR is in 0.5~30g/10min.
The glass fibre is the dedicated alkali-free short glass fiber of polypropylene, diameter 13um, the glass fibre
Surface is handled by silane coupling agent.
The compatilizer is that appearance is in faint yellow, the translucent liquor-saturated graft polypropylene particle of maleic acid, and grafting rate exists
0.5%-1.5%.
The adsorbent is natural aluminosilicate hydrochlorate, and aperture 0.1-1nm has suitable pore structure and surface texture,
There is strong adsorption capacity to adsorbate, the small-molecule substance of different molecular weight can be absorbed.
The antioxidant is Hinered phenols and thio ethers composite antioxidant.
The preparation method of the excellent glass fiber reinforced polypropylene composite material of a kind of above-mentioned low haze, heat-proof aging,
The following steps are included:
(1) it is put into high-speed mixer after weighing polypropylene, compatilizer, adsorbent and antioxidant in proportion, under room temperature
Stirring 10~30 minutes.
(2) step (1) mixed material is added to the main spout of double screw extruder, will be weighed by weight ratio
Glass fibre be added to the side spout of double screw extruder, squeezed out after 190 DEG C~230 DEG C sufficiently plasticizing mixing, be cooling
It is granulated the glass fiber reinforced polypropylene composite material excellent to get a kind of low haze of the invention, heat-proof aging.
Compared with prior art, the present invention have it is following the utility model has the advantages that
(1) it is not able to satisfy the mist degree requirement of lamp body based on conventional glass fibers enhancing PP, selectively uses
In the low homopolypropylene resin for melting finger, for enhancing PP low haze provide good material foundation guarantee.
(2) modified polypropene of the invention selects the efficiently low Hinered phenols distributed and thio ethers composite antioxidant, adds
Enter natural aluminosilicate hydrochlorate adsorbent, effectively adsorbs the small-molecule substance generated in raw material process, reach the mesh of low haze
Mark.
(3) present invention uses thermal stability more preferably compatilizer, in conjunction with Hinered phenols and thio ethers composite antioxidant, institute
The sample of acquisition has and the superior ageing-resistant performance of comparative sample.
Specific embodiment
Technical solution of the present invention is further illustrated below by preferred embodiment, is not violating spirit of the invention
Under, the present invention should be not limited to the content that following experimental example is specifically expressed.
The embodiment of the present invention is raw materials used:
PP: in it is low melt finger homopolypropylene, Samsung petro-chemical corporation, South Korea, melt index MFR be 12g/10min (230 DEG C,
2.16Kg)。
Glass fibre: 305K, Chongqing Polycomp International Co., Ltd.
Compatilizer: 1001, the bright company of Puli, grafting rate is 1.2%.
Adsorbent: CF-X01, Wuhan Ling Hui high molecular material Co., Ltd.
Antioxidant: the thio ethers 412S of Hinered phenols 1010/ is used in mixed way in 1:2 ratio, self-control.
Properties of product test method:
Tensile property: 527 method of ISO, 50 mm/min of tensile speed are pressed.
Bending property: 178 method of ISO, 2 mm/min of test speed are pressed.
Notch impact strength: 179 method of ISO, 4 millimeters thick samples are pressed.
Mist degree test: being tested by VW-50181 standard with PV 3015, and test value≤50ug/g is qualification.
Degradation: preparation standard tensile batten and notch shock batten, by DIN53497 progress degradation, 150 DEG C
Baking oven places 1000h, the tensile strength and notch impact strength of batten after testing experiment.
Embodiment 1-4
Polypropylene PP is weighed by the weight percent of embodiment 1-4 described in table 1, glass fibre 305K, compatilizer 1001,
Adsorbent CF-X01, homemade composite antioxidant.
Preparation method: (1) by polypropylene PP, compatilizer 1001, adsorbent CF-X01, homemade composite antioxidant is in proportion
It is put into high-speed mixer after weighing, is stirred 10~30 minutes under room temperature.(2) step (1) mixed material is added to double
The main spout of screw extruder, will glass fibre 305K weighed by weight ratio, be added to the side feed of double screw extruder
Material mouth squeezes out after 190 DEG C~230 DEG C sufficiently plasticizing mixing, cooling granulation is to get a kind of low haze of the invention, heat-resisting old
Change excellent glass fiber reinforced polypropylene composite material, standard testing sample is prepared using injection molding machine, test result is shown in Table 1.
Table 1: the performance test results
As can be seen from Table 1, the mist degree test value of comparative example Hostacom G3N01 is apparently higher than embodiment 2；And it is old
Tensile strength and notch impact strength conservation rate after change are lower than embodiment 2,3.The 34 μ g/g of haze value of embodiment 2 is lower than implementation
85 μ g/g of example 3, this shows that adsorbent CF-X01 effectively adsorbs the small-molecule substance generated in raw material process, reaches low
The target of mist degree.
For the present invention by the low homopolypropylene for melting finger in selecting, the efficient low Hinered phenols distributed and thio ethers are compound
Antioxidant adds natural aluminosilicate hydrochlorate adsorbent, effectively adsorbs the small-molecule substance generated in raw material process, reach vehicle
High request of the lamp housing for material low haze；Thermal stability more preferably compatilizer is selected simultaneously, in conjunction with efficient compound antioxygen
Agent makes sample obtained have superior ageing-resistant performance.
Claims (7)
1. the excellent glass fiber reinforced polypropylene composite material of a kind of low haze, heat-proof aging, by pressing quality percentage below
Raw material than meter forms: polypropylene 40%~85%, glass fibre 10~50%, compatilizer 2~10%, adsorbent 0.5-2%,
Antioxidant 0.2%~1%.
2. the excellent glass fiber reinforced polypropylene composite material of low haze according to claim 1, heat-proof aging, special
Sign is: the acrylic resin be in the low homopolypropylene for melting finger, melt index under 230 DEG C/2.16KG test condition
MFR is in 0.5~30g/10min.
3. the excellent glass fiber reinforced polypropylene composite material of low haze according to claim 1, heat-proof aging, special
Sign is: the glass fibre is the dedicated alkali-free short glass fiber of polypropylene, diameter 13um, the glass fibers dimension table
Face is handled by silane coupling agent.
4. the excellent glass fiber reinforced polypropylene composite material of low haze according to claim 1, heat-proof aging, special
Sign is: the compatilizer is that appearance is in faint yellow, the translucent liquor-saturated graft polypropylene particle of maleic acid, and grafting rate exists
0.5%-1.5%.
5. the excellent glass fiber reinforced polypropylene composite material of low haze according to claim 1, heat-proof aging, special
Sign is: the adsorbent is natural aluminosilicate hydrochlorate, and aperture 0.1-1nm has suitable pore structure and surface texture, right
Adsorbate has strong adsorption capacity, and the small-molecule substance of different molecular weight can be absorbed.
6. the excellent glass fiber reinforced polypropylene composite material of low haze according to claim 1, heat-proof aging, special
Sign is: the antioxidant is Hinered phenols and thio ethers composite antioxidant.
7. according to claim 1-6 it is one of any described in low haze, heat-proof aging it is excellent glass fiber reinforced polypropylene it is compound
The preparation method of material, which comprises the following steps:
(1) it is put into high-speed mixer after weighing polypropylene, compatilizer, adsorbent and antioxidant in proportion, is stirred under room temperature
10~30 minutes.
(2) step (1) mixed material is added to the main spout of double screw extruder, it will glass weighed by weight ratio
Glass fiber is added to the side spout of double screw extruder, squeezes out after 190 DEG C~230 DEG C sufficiently plasticizing mixing, cooling granulation,
Up to the excellent glass fiber reinforced polypropylene composite material of a kind of low haze of the invention, heat-proof aging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811635152.3A CN109705466B (en) | 2018-12-29 | 2018-12-29 | Glass fiber reinforced polypropylene composite material with low haze and excellent thermal aging resistance and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811635152.3A CN109705466B (en) | 2018-12-29 | 2018-12-29 | Glass fiber reinforced polypropylene composite material with low haze and excellent thermal aging resistance and preparation method thereof |
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| Publication Number | Publication Date |
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| CN109705466A true CN109705466A (en) | 2019-05-03 |
| CN109705466B CN109705466B (en) | 2022-04-08 |
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Cited By (3)
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| CN113045871A (en) * | 2020-12-22 | 2021-06-29 | 上海普利特复合材料股份有限公司 | Low-precipitation, low-haze and high-weather-resistance glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN114230921A (en) * | 2021-12-28 | 2022-03-25 | 上海普利特复合材料股份有限公司 | Low-dielectric high-thermal-conductivity flame-retardant glass fiber reinforced polypropylene material and preparation method thereof |
| CN114605737A (en) * | 2022-03-15 | 2022-06-10 | 国高材高分子材料产业创新中心有限公司 | PP-based standard sample for detecting bending property and preparation method thereof |
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| CN114230921A (en) * | 2021-12-28 | 2022-03-25 | 上海普利特复合材料股份有限公司 | Low-dielectric high-thermal-conductivity flame-retardant glass fiber reinforced polypropylene material and preparation method thereof |
| CN114605737A (en) * | 2022-03-15 | 2022-06-10 | 国高材高分子材料产业创新中心有限公司 | PP-based standard sample for detecting bending property and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN109705466B (en) | 2022-04-08 |
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